Non-grain-raising stain compositions and articles prepared therefrom



N ON-GRAlN-RAISIN G "STAIN COMPOSITIONS AND ARTICLES PREPARED THEREFROM Paul A. Blachman, Reading,.Pa., assignor to The Glidden Company, Cleveland, Ohio, a corporation of Ohio No Drawing. Application March 30, 1955 Serial No. 498,093

3 Claims. -(Cl. 106 34) This invention relates to improved non-grainrraising stains for WOOd and like'cellulosic construction materials.

It relates particularly to novel organic solvent solutions of metallized dyes of the metachrome azo type described *more specifically hereinafter, which solutions are suitable" for: use in staining wood or in coloring organic'coatings, e. .g., in preparing shading lacquers and *colored transparent lacquers.

Accordingly, the primary object of'my'inventionis to provide novel non-grain-raising stains for wood and related compositions.

Another object isto 'provide' novel articles'prepared from said stains and/ or compositions.

These and other objects will be apparent from the following description of my invention.

I have found that the premetallized, -e. g., metachrome, azo dyestuffs of U. '8. Patent 'No. 2,551,056, which are presently available for use'in dyeing wool, silk, nylon and like non cellulosic textile materials, 'can be dissolved in diverse organic solvents, such as alcohols and mixtures of alcohols with esters, ketonesand aromatic hydrocarbons to provide solutions of suflicient strength to be useful in staining wood. Since lacquersand ureaalkyd'loW-bake synthetic coatings conventionally contain solvents of the types mentioned in 'appropriateproportions for dissolving moderateamounts'of the dyes, the dyes can be used for coloring such lacquers thereby to provide clear, colored lacquer films. A wide range of colors is available in the dyes and can be dissolved in solvents or lacquers, and I have foundthat the resulting solutions give stained or colored films having good resistance to fading in sunlight when compared With the acid dyestuffs normally used in non-grain-raising'stains. When the solutions are used for staining Wood, they provide stained surfaces of exceptional depth and clarity of color, and impart a three-dimensional color effect usually attainable only by multiple staining operations. The stains dry rapidly, at room temperature, and the stained wood can be coated with conventional materials as soon as the stain is dry, without any detrimental elfects. When the dyes are dissolved in lacquer coatings, they donotretard the drying rate of the latter appreciably and have no adverse effects on the structure of the resulting film.

The metallized azo dyes which I have referred to above are the complex chromium compounds of monoazo dyestutfs having the formula A"representsiafbenzene nucleus B represents the radical of a member selected from the groupconsisting of phenoliqrnaphtholic and enolic i'proprietary names of lrgalan 'coupling components, and containing an OH-groupTin o-position to the azo group X represents a metallizable group selected from the group consisting of OH and COOH, in o-position to the azo group, and

n is one of the integers l and 2, the methyl sulfone group .being otherwise free from carboxylic, acid and .sulfonic acid groups Dyestufls of this type are currently available under the '(J. R. Geigy 'Co.), .Nyalan '(Nyanza Color and Chemical Co.), and Chromolan (National Aniline and Dyestufi Col).

The solvents appropriate for use inpreparing moderately "concentrated solutions of the-dyes include primary alcohols (alip'hatic=and/or aralkyl); polyhydric-alcohols, e. ig., glycols, :glycerine, -etc.; esters; glycol ethers; ketones;

and mixtures, zespecially mixtures with primary alcohols. The following list of solvents is representative but not limiting:

Methanol Ethanol Propanol Butanol Glycerine Ethylene glycol Propylene glycol Butylene glycol Ethylene glycol monoalkyl ethers, e. g., monomethyl,

monoethyl, monobutyl, etc.

'Diethylene glycol monoalkyl ethers Acetone Methyl ethyl ketone Methyl isobutyl ketone n-Butyl acetate Diacetone alcohol Mixtures of equal parts of methanol and'ethanol A mixture composed of 31 parts of methanol, 9.5 parts ethanol and 2.375 parts toluol The following examples illustrate the best embodiments of the invention presently known to me:

EXAMPLE 1 A dye concentrate was first made .utilizingthefollowing materials:

Denatured alcohol gallons '32 Nyalan Grey BL pounds 1.625

EXAMPLE 2 A dye concentrate was prepared'frorn:

Denatured alcohol gallons :64 Methanol "do :64 Nyalan-Red 3-G pounds... :10 Nyalan Bordeaux 2 BL do :1 Nyalan YellowGL do. 1

Nyalan Grey .BL .;d0. 1

'lhe' dyes were dissolved in the mixed solvents at about 100 'F.-and theresulting solution was allowed to stand for four hours. The solution was then decanted through a filter medium.

When the clear dye concentrate was applied at a spraying pressure of about 70 p. s. i. to birch wood, the wood exhibited an attractive red cherry color. The stained wood could be coated with lacquer sealer almost immediately, ;because :the; highspraying pressure ,yielded a dry stained surface.

EXAMPLE 3 A dye concentrate was prepared from: 1

Denatured alcohol gallons 42 Irgalan Grey BL ..pounds 2.5

, The dye was sifted into the alcohol with stirring, the alcohol being atroom temperature. Agitation was continued' until all of the dye had been dissolved. 1

Application of the dye concentrate to birch wood by spraying at 70 p. s. i. pressure yielded an attractive blue-grey color of excellent depth and clarity. The stain surface could be coated with lacquer and other sealers Denatured alc hol gallons.

EXAMPLE 5 V i A cherry cordovan shading lacquer was prepared as follows:

SolutionA Nyalan Grey BL pounds 1% Nyalan Bordeaux 2 BL do Nyalan YellowZRL do.. Methanol gallons-.. 2 /2 Dissolve dyes in methanol at 100 F. Settle and decant.

I Solution B 801 P Amberol (Rohm & Haas) maleic treated rosin ester pounds 2.0 Toluol gallons 6.25

Dissolve: I

5-6" R. S. nitrocellulose .pounds 9.3 Di-butyl phthalate gallons .125 Isopropyl acetate do 1.95 Methyl ethyl ketone do 5.3125 Methyl isobutyl ketone do .1875 Tnlunl do 6.00

Irgalan Brown 3 BL pound s 1.625

The dye was sifted into the alcohol at room temperature with agitation and agitation was continueduntil-the dye had dissolved. The resulting solution was'allowed to 1 stand over night and then was decanted through a filter.

Similar control panels stained with typical stains heretofore used were similarly exposed. After one Week the panels of Examples -14 revealed no apparent change in color, While the control panels had been bleached very noticeably. Even a months exposure showed little change in the color of the panels of Examples1-4.

It will be noted in Examples l-4 that no binder is employed in those stains. Nevertheless, when the stains are sprayed at high or low spraying pressure and have become dry, the stained surface is remarkably resistant to abrasion. considerable pressure without removing the color. However, it should be coated with a clear protective film in order to achieve the durability which is commonly expected nowadays. A lacquer sealer serves this purpose,

monazo dyestufi having the formula It can be rubbed with the fingers under y although other protective coatings such as clear alkyds p can. be used. The lacquer-type coatings are preferred, however, since they. enhance the depth of color and the clarity. This is due partly to the fact that the wet lacquer film dissolves a small part of the dye, thereby producing a colored coating in situ. Alkyd-type coatings tend to give less clarity and depth."

The sealer which is applied directly to the stained surface can, of course, be further coated with additional clear films of any desired chemical nature so long as they develop satisfactory intercoat adhesion to the sealer.

My new stains are outstanding because they make it possible to achieve in a two-step staining and sealing operation a quality of clarity,-depth and brilliance seldom encounteredwith the stains-conventionally used heretofore. Moreover, the dyespermit a widerrange of colors, shades and tones than was possible formerly, along with greatly enhanced resistance to fading.

The following is an illustration of a shading lacquer.

Dissolve and add to Amberol solution.

Add solution A to solution, B slowly with agitation. The

.resulting lacquer has an'intense, transparent black color dyestufi, this lacquer will not migrate from a film on furniture into cloth *covers placedover it. It will be many times more permanent in relation to direct sunlight. Unlike shading lacquers made from aciddyestufis, it will exhibit much better color stability in the package as well as resistance to fading in sunlight;

The oil-soluble colors are-based on stearic/oleic fixatives and, as such, tend to retard dry rateas well as to destroy the integrity of the resultant film. My invention does not have this detrimental efiect.

The same formulation at; higher solids can be used as a transparent lacquer coating suitable for glass, metal,

wood or leather. 7

Having now described my invention, what I claim is: 1. As a novel composition, (I) an organic solvent solution of at least one complex chromium compound of a X represents a metallizable group selected from the group consisting of'OH and COOH, in o-position to the azo group, and

n is one -'of the integers 1 and 2, the methyl sulfone group being otherwise free from carboxylic acid and sulfonic acid groups I and (II) a binder component composed essentially of :lacquer-type film-forming materials.

2. As a novel article of manufacture, a body having a surface portion -thereof dyed and coated with a film obtainedby coating said portion, with a liquid film of the composition as claimed in claim 1, and then drying 3. As a novel article of manufacture, a wood member having a surface portion thereof stained with a nongrain-raising stain for wood composed essentially of an organic solvent solution of at least one complex chrm mium compound of a monazo dyestuff having thefor' mula 1 7 2,820,712 5 6 wherein n is one of the integers 1 and 2, the methyl sulfone group being otherwise free from carboxylic acid and sulfonic A represents a benzene nucleus acid groups B represents the radical of a member selected from the group consisting of phenolic, naphtholic and enolic coupling components, and containing an OH group in 5 References Cited in the file of this Patent o-position to the azo group UNITED STATES PATENTS X represents a metallizable group selected from the group 25 603 L b D 17 1940 consisting of OH and COOH, in o-position to the 2120 4:372 i i g;Z:1";211112221"; 2s 1941 gmupand 10 2,551,056 Schetty May 1, 1951 

1. AS A NOVEL COMPOSITION, (I) AN ORGANIC SOLVENT SOLUTION OF AT LEAST ONE COMPLEX CHROMIUM COMPOUND OF A MONAZO DYESTUFF HAVING THE FORMULA 